Glass fiber structure designed to reinforce bonded abrasive articles

ABSTRACT

The invention relates to a structure based on glass fiber coated with a resin composition designed to reinforce bonded abrasive articles, the resin composition including the following constituents in the proportions indicated, expressed in percentage by weight of solid matter:
         75 to 98% of a mixture of at least one novolac having a glass transition temperature lower than or equal to 60° C. and at least one novolac having a glass transition temperature above 60° C.,   0.5 to 10% of at least one wax,   0 to 3.5% of at least one plasticizing agent.

This application is a Divisional application of U.S. application Ser.No. 12/665,142 filed Feb. 23, 2010, the entire content of which isincorporated herein by reference, and now U.S. Pat. No. 8,545,584, whichis a 371 of International Application No. PCT/FR08/51088, filed on Jun.18, 2008, which claims priority of French Application No. 0755818, filedon Jun. 18, 2007.

The present invention relates to the field of abrasives. It relates moreprecisely to a structure based on glass fiber coated with a resincomposition designed to reinforce bonded abrasive articles, inparticular grinding wheels, the resin composition used for coating thisstructure and the bonded abrasive articles incorporating such astructure.

Abrasive articles contain a multitude of abrasive particles solidlybound together by a binder. These articles are widely employed formachining parts made of various materials, particularly in cut-off,deburring, surface grinding and polishing operations.

In a conventional manner, the following may be distinguished:

-   -   coated abrasives that comprise a flexible backing on the surface        of which abrasive particles are distributed fixed in a binder.        The flexible backing may be a sheet of paper or a network of        fibers, for example, a mat, a felt or a fabric. These articles        may adopt various forms, sheets, disks, belts, cones, etc.    -   bonded abrasives that are obtained from a mixture of abrasive        particles and a binder, formed and compacted by molding under        pressure. They consist essentially of abrasive grinding wheels.

Bonded abrasive articles to which the invention more particularlyrelates are abrasive grinding wheels for cutting of hard materials, inparticular steel. These grinding wheels are employed on machinesoperating at a high peripheral speed, and on account of this must beable to withstand high mechanical stresses produced by the latter.

In particular, it is important for the following requirements to besatisfied:

-   -   the abrasive particles must be suited to the nature of the        material to be processed: they must be sufficiently durable so        as not to crumble in contact with said material, and to preserve        sufficiently sharp edges so that they can cut it;    -   the binder must have good tensile strength so that the abrasive        particles remain bonded to it and are not torn out under the        effect of centrifugal force. In addition the binder should be        able to withstand high temperatures that result from high        friction with the material to be processed; the binder must        neither flow nor be degraded under the effect of heat,    -   the abrasive grinding wheel should not wear prematurely nor        burst; it must retain its initial dimensional properties for as        long as possible so that cutting is carried out under good        conditions.

It is usual to consolidate the abrasive grinding wheel by incorporatingtherein at least one structure based on reinforcing yarns, particularlyglass fiber yarns that may be for example in the form of a fabric.

However, given that bare glass fiber has virtually no adhesion to thebinder, it is necessary to coat the structure of the glass fiber with aresin composition that ensures a bond between the glass and the binder.

In a known manner, the reinforcing structure is obtained by passing theglass fiber through a bath with a resin composition consisting of analcoholic solution containing of the order of 70% by weight of resin,and then passing it between two rollers so as to remove the excessresin, and finally in a chamber heated to a temperature of the order of100 to 145° C. for a maximum of a few minutes so as to reduce thequantity of solvent based on the resin to a value of approximately 5% to10%. The reinforcing structure obtained in this way is collected in theform of a winding, for example a reel, or is cut up either into sheetsor directly into the desired shape and dimensions of the final grindingwheel, for example by means of a punch.

In a subsequent step, the abrasive grinding wheel is obtained accordingto the method that consists of placing in a mold, alternately, severallayers of the mixture of abrasive particles and binder on the one hand,and of the reinforcing structure on the other hand, and of molding theassembly by compression either hot or cold. After demolding, the articleobtained is treated thermally under temperature conditions enabling thebinder to be crosslinked and finally to obtain the abrasive grindingwheel.

The resin compositions most commonly used for the production of theaforementioned reinforcement structures comprise at least onethermosetting resin chosen from:

-   -   urea-aldehyde resins, for example a urea-formaldehyde resin        (GB-A-419 812),    -   phenolic resins, for example a novolac associated with a cross        linking agent hexamethylenediamine, (GB-A-1 151 174) or mixture        of a resol in solution and solid novolac associated with a        crosslinking agent, hexamethylenetetramine (U.S. Pat. No.        4,338,357), and    -   mixtures of urea-aldehyde resins and phenolic resins, for        example a urea-formaldehyde prepolymer and a phenolic resin in        the A stage (U.S. Pat. No. 4,038,046) or a urea-formaldehyde        resin and a resol in the presence of an acid catalyst (U.S. Pat.        No. 5,551,961).

The aforementioned resin compositions are not costly and they enablereinforcing structures to be obtained that exhibit good properties,particularly in terms of flexibility and adhesive power.

It is in point of fact important that the structure has a sufficienthigh flexibility, that is to say the resin is not too “hard” so that thecutting operations as previously described can be carried out underacceptable conditions, by generating the least possible dust and byoperating so that the resin is not removed in the vicinity of the cutedges of the structure (glass is not laid bare).

However, it is also necessary for the adhesive power (also called“tack”) not to be too high, so as not to soil the cutting tools, tolimit contamination during storage by dust that adheres to thestructures and to avoid having to place an antiblocking material on thestructure before it is reeled up or between cut structures.

As regards the regulations, it is necessary to have non-polluting resincompositions available, that is to say those that contain—but also thatgenerate during application to the reinforcement structure orsubsequently—the fewest possible compounds considered as being able toharm human health or the environment.

In this respect, the aforementioned resin compositions do not givecomplete satisfaction.

Urea-formaldehyde resins are not heat-stable and degrade whileliberating formaldehyde as soon as the temperature exceeds 100° C.Formaldehyde may thus be released when the reinforcing structure isproduced, during drying in the heated chamber and when the abrasivegrinding wheel is used.

Phenolic resins are obtained by the condensation of phenol andformaldehyde, either in a formaldehyde/phenol molar ratio less than 1 inthe presence of an acid catalyst (novolacs) or in a formaldehyde-phenolmolar ratio greater than 1 in the presence of a basic catalyst (resols).Novolacs contain virtually no free formaldehyde but they are used inconjunction with a crosslinking catalyst such as hexamethylenediamineand hexamethylenetetramine that is not heat-stable and generatesemissions of formaldehyde and ammonia during the production of thereinforcing structure and use of the abrasive grinding wheel. Resolscontain free formaldehyde in a relatively high quantity.

The object of the present invention is to develop a resin compositioncapable of coating a glass fiber structure designed to reinforce bondedabrasive articles, and in particular grinding wheels, that gives thestructure great flexibility and low adhesive power, and that limits therisk of polluting emission of formaldehyde and nitrogen-containingcompounds.

This objective is achieved by virtue of the invention that provides areinforcing structure coated with a resin composition comprising thefollowing constituents in the proportions indicated, expressed as apercentage by weight of solid matter:

-   -   75 to 98% of a mixture of a least one novolac having a glass        transition temperature lower than or equal to 60° C. and at        least one novolac having a glass transition temperature above        60° C.,    -   0.5 to 10% of at least one wax,    -   0 to 3.5% of at least one plasticizing agent.

The combination of novolacs having different glass transitiontemperatures and wax has proved to be particularly valuable forproducing a resin composition capable of coating a glass fiber structurethat is suitable for the reinforcement of bonded abrasives. Theproperties of the novolacs and wax are in point of fact complementary.

The novolac having the lower glass transition temperature givesflexibility to the structure and makes it possible to have a high levelof flexibility. It makes it possible to compensate for the too highrigidity of the novolac with a higher glass transition temperature andin this way to adjust the flexibility to the desired level.

As already mentioned, it is important to have high flexibilities so thatthe structure can be correctly cut, in particular without the resincomposition being able to “crumble away” in the region of the edges,leaving the glass bare.

Preferably, the novolac having the lower glass transition temperature,that is to say below or equal to 60° C., represents 50 to 80% by weightof the mixture of novolacs.

Advantageously, the glass transition temperature of the novolac with thelower glass transition temperature is above 40° C. Similarly, the glasstransition temperature of the novolac having the higher glass transitiontemperature is above or equal to 80° C., and advantageously lower thanor equal to 100° C.

Novolacs according to the invention may be chosen from novolacs known toa person skilled in the art obtained by reacting a phenolic compound,preferably phenol, and an aldehyde, preferably formaldehyde, in thepresence of an acid catalyst (pH of the order of 4 to 7). Preferably,the formaldehyde/phenol molar ratio varies from 0.75 to 0.85. The choiceof novolac is made according to the desired glass transitiontemperature.

Novolacs that may be used within the context of the invention containless than 0.1% by weight of free formaldehyde, and preferably less than0.05%.

Wax acts as an “antiblocking” agent and makes it possible to compensatefor the high adhesive power of the novolac that has the lower glasstransition temperature. As already said, an adhesive power that is nottoo high makes it possible, on the one hand, to preserve cut reinforcingstructures in a very valuable state of cleanliness that avoidscontamination by dust, and on the other hand makes it possible to handlethese cut structures with a minimum risk of their adhering to each otherunder moderate pressure, notably during storage.

The wax is chosen from paraffin waxes, for example polyethylene orpolypropylene waxes, and ethylenebisamide waxes, notablyN,N′-ethylenebis(steramide). Advantageously, the wax ismicrocrystalline.

Preferably, the wax content does not exceed 5% by weight of solid matterof the resin composition, and advantageously is less than or equal to3%.

The plasticizing agent contributes to an improvement to the flexibilityof the resin composition. As examples of such agents, mention may bemade of alkylphosphates, phthalates, triethanolamine, oils andpolyhydric alcohols, notably glycerol and glycols.

Preferably, the plasticizing agent content does not exceed 1% by weightof solid matter of the resin composition.

It should be noted that the resin composition coating the reinforcingstructure according to the invention does not contain any crosslinkingagent, which is particularly advantageous since novolacs may preservetheir initial thermoplastic nature. The resin composition is not likelyto change with time so that the reinforcing structure may be stored fora very long period, which is a supplementary advantage compared withknown resin compositions.

The reinforcing structure may be composed of continuous glass yarns,preferably in the form of a nonwoven such as a web or a mat, a mesh orfabric, or of a mat of cut strands.

The glass yarns are yarns called “reinforcing”, produced industriallyfrom molten glass threads flowing from the multiple orifices of a die,these threads being drawn out mechanically in the form of continuousfilaments that are assembled into a base yarn and then collected byreeling on a rotating support.

The glass yarns according to the invention are thus base yarns, andproducts derived from these yarns, in particular assemblies of thesebase yarns in laminates. Such assemblies are obtained by simultaneouslyunreeling several coils of base yarns and then assembling them intomeshes that are reeled onto a rotating support. The glass yarns mayundergo a twisting operation in order to produce textile yarns forproducing fabrics.

The glass yarns consist of glass filaments of which the diameter mayvary widely, for example from 9 to 24 μm, preferably 9 to 17 μm.Advantageously, the glass yarns have a count (or linear mass) of between34 and 4800 tex, preferably between 34 and 1200 tex.

The yarns may consist of any type of glass, in particular E, C and AR(alkali-resistant). Preferably, they consist of E glass.

According to a preferred embodiment, the structure is a fabric composedof glass yarns, having a grammage that varies from 100 to 1000 g/m².

The resins composition itself, before it is applied to the reinforcingstructure, also constitutes an object of the invention. Thus, the resincomposition comprises the following compounds, expressed in percentageby weight:

-   -   25 to 55% of at least one novolac having a glass transition        temperature less than or equal to 60° C.,    -   10 to 30% of at least one novolac having a glass transition        temperature above 60° C.,    -   0.5 to 6.5% of at least one wax,    -   0 to 2.5% of at least one plasticizing agent,    -   25 to 45% of at least one alcohol,    -   0 to 15% of water.

As an alcohol according to the invention, mention may be made ofmethanol, ethanol, isopropanol and mixtures of these alcohols.

The resin composition may be prepared by simply mixing the constituentsin a suitable vessel, advantageously provided with stirring means. Thenovolacs are preferably in the form of a solution in ethanol or amixture of ethanol and methanol, the wax is a dispersion in water andthe plasticizing agent is liquid.

As the case may be, the resin composition may contain additives such asemulsifiers, pigments, fillers, antimigration agents, coalescing agents,wetting agents, biocides, organosilanes, antifoam agents, colorants andanti-oxidant agents. The additives content does not exceed 3% of solidmatter of the resin composition.

Production of the coated reinforcing structure is carried outcontinuously by passing it first of all through an impregnating bathconsisting of the liquid resin composition, and then through the nip ofa calendering device composed of two rollers, which makes it possible toadjust the resin composition content to a value close to 30% by weightof solid matter, and finally through a heated chamber so as to removepart of the solvent. Preferably, the chamber comprises a first zoneheated to a temperature of the order of 130° C. and at least one secondzone heated to a temperature of the order of 110° C., the dwell time ofthe reinforcing structure in both zones being generally less than tenminutes, preferably varying from 30 seconds to 3 minutes. Preferably,the percentage solvent in the reinforcing structure is less than 12% andadvantageously less than 10%. The reinforcing structure obtained is thencollected in the form of a reel and cut up either into sheets ordirectly in the shape and dimensions of the final abrasive grindingwheel, these cut structures being then stored in the form of stacks.

The reinforcing structure according to the invention may be used inparticular for producing bonded abrasive articles such as abrasivegrinding wheels, these articles thus constituting an object of theinvention.

These abrasive articles may be produced in particular according tocompression molding techniques known to a person skilled in the art. Forexample, the abrasive grinding wheels may be obtained by depositingseveral alternate layers of a granular mixture of abrasive particlesinside a mold, and the reinforcing structure previously cut up to thedimensions of the mold. The number of reinforcing structures variesaccording to the desired level of the performance for the abrasivegrinding wheel; generally, this number does not exceed 10.

The mold is put under pressure sufficient to form a “green” part thatexhibits cohesion so that it may be handled and processed in thefollowing steps without substantial modification to the shape anddimensions. The mold may be heated during compression (hot molding) to atemperature that is generally below 170° C. or even 150° C. The binderat this stage is in the non-crosslinked state.

The green part is removed from the mold and heated in an oven at atemperature enabling the binder to crosslink and to give a hardenedpolymer network that gives the part its final form. Crosslinking iscarried out according to a conventional curing cycle that consists ofbringing the green part to a temperature of the order of 100° C. and ofholding it at this temperature for 30 minutes to several hours so thatthe volatile products formed may be removed. The part is then heated toa temperature of the order of 200 to 250° C. for 10 to 35 hours.

The abrasive grinding wheel obtained in this way may be used in alltypes of application that require abrasive properties, for examplesanding, deburring, surface finishing operations, and more particularlythe cutting of hard materials, such as steel.

The examples given hereinafter enable the invention to be illustratedwithout however limiting it.

In these examples, the properties of the resin composition and thereinforcing structure were evaluated under the following conditions:

Resin

-   -   the glass transition temperature (Tg) was measured by DMTA        (Dynamic Mechanical Thermal Analysis).    -   the number average molar weight (M_(n)) and the weight average        molar weight (M_(w)) were determined by gel permeation        chromatography (GPC) under the following conditions:    -   stationary phase: Styragel® HR4E marketed by Waters, held at 30°        C.    -   mobile phase: tetrahydrofuran (THF)    -   detection: differential refractometry (ΔRI)    -   calibration: polystyrene standards

Resin Composition

-   -   the flexibility of the resin composition was measured as        follows: the resin composition (weight content in solid matter:        40 to 60%) was deposited on a piece of paper (dimensions: 20        mm×70 mm; grammage: 3600 g/m²) and a 200 μm thick layer was        spread out with the aid of a film spreader. The paper was dried        in a heated chamber at 140° C. for 1 minute. A free end of the        paper was fixed to a horizontal support and a weight of 2.8 g        was suspended from the other end. After 4 minutes, the angle θ        that the paper made to the horizontal was measured. The        flexibility was suitable when the value of the angle θ was above        or equal to 30°.    -   adhesive power was evaluated as follows: two cylindrical        aluminum studs were used with a circular cross section (area:        3.2 cm²). 0.2 ml of the resin composition was deposited on each        section and the studs were placed in a ventilated chamber heated        to 130° C. for 10 minutes. After cooling for 30 minutes at        ambient temperature, the studs were stored in a controlled        atmosphere (temperature: 22° C.; relative humidity 50%) for a        variable period. The surfaces coated with the resin composition        were placed in contact with each other while applying a pressure        of 50 N for one minute. The assembly was placed on a tensile        machine and the force necessary to separate the studs was        measured. The adhesive power was satisfactory when the force was        less than 30 N.

Reinforcing structure

-   -   amount of dust: a sample of the reinforcing structure was        weighed and folded manually along a length of 44 to 46 cm. The        sample was unfolded and weighed. The percentage of loss in        weight of sample corresponded to the amount of dust. The amount        of dust is a parameter that makes it possible to evaluate the        ability to be cut: it is considered as being acceptable when its        value is less than 2%.    -   adhesive power: two reinforcing structures in the form of a 10        to 12 cm diameter disk were superimposed and a temperature of 50        N was applied for one minute. The sample was placed on a tensile        machine and the force necessary to separate the structures was        measured. The adhesive power was satisfactory when the force was        less than 5 N.    -   the tensile strength of the warp or weft was measured under the        conditions of ISO standard 3341 applicable to glass yarn up to        2000 tex. The value of the textile strength had to be greater        than 300 N.    -   the loss on ignition was measured under the conditions of ISO        standard 1887.

EXAMPLE 1

A resin composition was prepared comprising the following constituents:

(% by weight) (% solid matter) Novolac⁽¹⁾ (Tg around 40° C.) 50.0 76.47Novolac⁽²⁾ (Tg around 80° C.) 13.0 20.58 Polyethylene wax ⁽³⁾ 2.0 2.95Water 3.0 Alcohol 32.0

The resin composition had the following properties:

-   -   flexibility: 35°    -   adhesive power: 0 N at t=0        -   0.13 N at t+15 days        -   2.37 at t+30 days

EXAMPLE 2

A resin composition was prepared comprising the following constituents:

(% by weight) (% solid matter) Novolac⁽¹⁾ (Tg around 40° C.) 47.0 74.28Novolac⁽²⁾ (Tg around 80° C.) 13.0 20.00 Polyethylene wax ⁽³⁾ 3.5 5.72Water 5.5 Alcohol 31.0

The resin composition had the following properties:

-   -   flexibility: 35°    -   adhesive power: 0.80 N at t=0        -   1.20 N at t+15 days        -   1.35 at t+30 days

COMPARATIVE EXAMPLE 1

A resin composition was prepared under the conditions of example 1,modified in that it only contained the novolac⁽¹⁾:

(% by weight) (% solid matter) Novolac⁽¹⁾ (Tg around 40° C.) 65.0 100Alcohol 35.0

The resin composition had the following properties:

-   -   flexibility: >30°    -   adhesive power: 88.44 N at t=0

COMPARATIVE EXAMPLE 2

A resin composition was prepared under the conditions of example 1,modified in that it comprised the following constituents:

(% by weight) (% solid matter) Novolac⁽¹⁾ (Tg around 40° C.) 59.0 94.20Polyethylene wax ⁽³⁾ 3.5 5.80 Water 5.5 Alcohol 32.0

The resin composition had the following properties:

-   -   flexibility: >30°    -   adhesive power: 26.95 N at t=0

COMPARATIVE EXAMPLE 3

A resin composition was prepared under the conditions of example 1,modified in that it comprised the following constituents:

(% by weight) (% solid matter) Novolac⁽¹⁾ (Tg around 40° C.) 52.0 78.80Novolac⁽²⁾ (Tg around 80° C.) 14.0 21.20 Alcohol 34.0

The resin composition had the following properties:

-   -   flexibility: 35°    -   adhesive power: 34.40 N at t=0

EXAMPLE 3

This example illustrates the application of the resin composition in asemi-industrial installation.

A glass fiber fabric (grammage): 198 g/m²; warp thread: EC 204 tex s/z;weft thread RO 408 tex), 0.5 m wide, unwound from a reel, was disposedon a coating line operating continuously. On its path, the fabric passedinto an impregnating bath containing the resin composition and was thentreated in an oven comprising a first section heated to 125° C., and asecond section heated to 115° C., before being collected in the form ofa reel.

The resin composition comprised the following constituents:

(% by weight) (% solid matter) Novolac⁽¹⁾ (Tg around 40° C.) 50.0 77.15Novolac⁽²⁾ (Tg around 80° C.) 14.0 20.77 Polyethylene wax ⁽³⁾ 1.3 2.08Water 1.7 Alcohol 33.0 ⁽¹⁾Phenol-formaldehyde novolac: M_(n) = 829;M_(w) = 2176; ethanol solution at 65% by weight solid matter.⁽²⁾Phenol-formaldehyde novolac: M_(n) = 1247; M_(w) = 5779; solutionwith 70% by weight solid matter in a 25:5 ethanol:methanol mixture. ⁽³⁾Marketed under the reference “Hydrocer 69” by Shamrock.

The reinforcing fabric had the following properties:

-   -   Amount of dust: 0.03%    -   Adhesive power: 0 N    -   Tensile strength (warp thread): 304 N    -   Tensile strength (weft thread): 343 N    -   Loss on ignition: 30%    -   Volatile compounds content: 4.65%

The invention claimed is:
 1. A resin composition, comprising the following, expressed in percentage by weight 25 to 55% of at least one first novolac having a glass transition temperature lower than or equal to 60° C., 10 to 30% of at least one second novolac having a glass transition temperature above 60° C., 0.5 to 6.5% of at least one wax, 0 to 2.5% of at least one plasticizing agent, 25 to 45% of at least one alcohol, 0 to 15% of water, wherein the resin composition does not comprise a crosslinking agent.
 2. The resin composition of claim 1, wherein the alcohol is methanol, ethanol, isopropanol, or a mixture thereof.
 3. The resin composition of claim 1, wherein the first novolac has a glass transition temperature above 40° C.
 4. The resin composition of claim 1, wherein the second novolac has a glass transition temperature above or equal to 80° C.
 5. The resin composition of claim 1, wherein the second novolac has a glass transition temperature below or equal to 100° C.
 6. The resin composition of claim 1, wherein the first novolac and the second novolac are obtained by a process comprising reacting phenol and formaldehyde in a formaldehyde/phenol molar ratio that varies from 0.75 to 0.85.
 7. The resin composition of claim 1, wherein the wax is at least one paraffin wax, at least one ethylenebisamide wax or a mixture thereof.
 8. The resin composition of claim 1, wherein the wax content does not exceed 5% by weight of solid matter of the resin composition.
 9. The resin composition of claim 1, wherein the wax content does not exceed 3% by weight of solid matter of the resin composition.
 10. The resin composition of claim 1, wherein the plasticizing agent is alkylphosphate, phthalate, triethanolamine, oil, polyhydric alcohol or a mixture thereof.
 11. The resin composition of claim 1, wherein the plasticizing agent content does not exceed 1% by weight of solid matter of the resin composition.
 12. The resin composition of claim 1, wherein the wax is a paraffin wax, wherein the paraffin wax is polyethylene or polypropylene.
 13. The resin composition of claim 1, wherein the wax is an ethylenebisamide wax, wherein the ethylenebisamide wax is N,N′-ethylenebis (steramide). 